Aromatic alkylation process using UZM-5 and UZM-6 aluminosilicates

ABSTRACT

A process for alkylation of aromatic compounds using a new family of related crystalline aluminosilicate zeolites has been developed. These zeolites are represented by the empirical formula: 
     
       
         M m   n+ R r   p+ Al (1−x) E x Si y O z   
       
     
     where M is an alkali or alkaline earth metal such as lithium and strontium, R is a nitrogen containing organic cation such as tetramethyl-ammonium and E is a framework element such as gallium.

FIELD OF THE INVENTION

This invention relates to an alkylation process using a family ofrelated crystalline aluminosilicate zeolites, examples of which havebeen designated UZM-5, UZM-5P and UZM-6. These zeolites are structurallydifferent from other zeolites.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which have a three dimensional oxide framework formedfrom corner sharing AlO₂ and SiO₂ tetrahedra. Numerous zeolites, bothnaturally occurring and synthetically prepared are used in variousindustrial processes. One such process is the alkylation of aromaticswith olefins and especially the alkylation of benzene with ethylene orpropylene. The reaction between benzene and propylene produces mostlycumene. Cumene is an important industrial compound because it is asource of phenol, acetone, which are obtained by the oxidation of Cumeneand subsequent acid-catalyzed decomposition of the intermediatehydroperoxide. Acid catalysts are used to catalyze this reaction withthe most common catalysts being zeolites and particularly zeolite beta.

Applicants have synthesized a new family of crystalline aluminosilicatezeolites which have good activity for the alkylation of aromatics. Thesecrystalline zeolitic compositions have a unique x-ray diffractionpattern and have an empirical formula on an anhydrous basis in terms ofmolar ratios of

M_(m) ^(n+)R_(r) ^(p+)Al_((1−x))E_(x)Si_(y)O_(z)

where M is at least one exchangeable cation selected from the groupconsisting of alkali and alkaline earth metals, “m” is the mole ratio ofM to (Al+E) and varies from about 0 to about 1.2, R is anitrogen-containing organic cation selected from the group consisting ofquaternary ammonium ions, protonated amines, protonated diamines,protonated alkanolamines, quaternary alkanolammonium ions anddiquaternary ammonium ions, and mixtures thereof, “r” is the mole ratioof R to (Al+E) and has a value of about 0.25 to about 3.0, E is anelement selected from the group consisting of Ga, Fe, Cr, In and B, “x”is the mole fraction of E and varies from 0 to about 0.5, “n” is theweighted average valence of M and has a value of +1 to about +2, “p” isthe weighted average valence of R and has a value of +1 to about +2, “y”is the mole ratio of Si to (Al+E) and varies from about 5 to about 12.and “z” is the mole ratio of 0 to (Al+E) and has a value determined bythe equation:

z=(m·n+r·p+3+4·y)/2.

Specific members of this family of zeolites are UZM-5, UZM-5P and UZM-6.

SUMMARY OF THE INVENTION

This invention relates to a process for the alkylation of aromaticcompounds using a new family of zeolites. Accordingly, one embodiment ofthe invention is a process for alkylating an aromatic compoundcomprising reacting under alkylation conditions and under at leastpartial liquid phase conditions an olefin with an alkylatable aromaticcompound to provide an alkylated compound in the presence of acrystalline aluminosilicate zeolite having a composition in the assynthesized and anhydrous form in terms of mole ratios of the elementsgiven by:

 M_(m) ^(n+)R_(r) ^(p+)Al_((1−x))E_(x)Si_(y)O_(z)

where M is at least one exchangeable cation selected from the groupconsisting of alkali and alkaline earth metals, “m” is the mole ratio ofM to (Al+E) and varies from about 0 to about 1.2, R is anitrogen-containing organic cation selected from the group consisting ofprotonated amines, protonated diamines, protonated alkanolamines,quaternary ammonium ions, diquaternaryammonium ions, quaternizedalkanolamines and mixtures thereof, “r” is the mole ratio of R to (Al+E)and has a value of about 0.25 to about 3.0, E is an element selectedfrom the group consisting of Ga, Fe, Cr, In and B, “x” is the molefraction of E and varies from 0 to 0.5, “n” is the weighted averagevalence of M and has a value of about +1 to about +2, “p” is theweighted average valence of R and has a value of +1 to about +2, “y” isthe mole ratio of Si to (Al+E) and varies from about 5 to about 12 and“z” is the mole ratio of O to (Al+E) and has a value determined by theequation:

z=(m·n+r·p+3+4·y)/2

the zeolite characterized in that it has at least two x-ray diffractionpeaks, one at a d-spacing of 3.9±0.12 Å and one at 8.6±0.20 Å.

In a particular embodiment, the zeolite catalyst has been designatedUZM-5 and has the x-ray diffraction pattern having at least thed-spacings and intensities set forth in Table A:

TABLE A UZM-5 2-θ d(Å) I/I_(o) % 6.31-5.89 14.00-15.00 w-m 7.96-7.5811.10-11.65 m-s 10.40-10.01 8.50-8.83 w-m 12.11-11.59 7.30-7.63 m16.10-15.53 5.50-5.70 m-vs 19.28-18.55 4.60-4.78 w-m 22.26-21.603.99-4.11 m 23.20-22.43 3.83-3.96 w-s 24.16-23.33 3.68-3.81 vs30.48-29.55 2.93-3.02 w-m 31.94-30.92 2.80-2.89 w-m 44.83-43.472.02-2.08 w

One specific embodiment involves the alkylation of benzene withpropylene to give cumene.

Another embodiment of the invention is a transalkylation processcomprising reacting under transalkylation reaction conditions apolyalkylated aromatic compound with a nonalkylated aromatic compound inthe presence of the zeolites described above, wherein at least one alkylgroup is transferred from the polyalkylated aromatic compound to thenonalkylated aromatic compound.

These and other objects and embodiments will become more apparent afterthe following detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

An essential feature of applicants' process is a new family of zeolites.In its as-synthesized form this family of zeolites has a composition onan anhydrous basis that is represented by the formula:

 M_(m) ^(n+)R_(r) ^(p+)Al_((1−x))E_(x)Si_(y)O_(z)

Where M is an exchangeable cation and is selected from the groupconsisting of alkali and alkaline earth metals. Specific examples of theM cations include but are not limited to lithium, sodium, potassium,cesium, strontium, calcium, magnesium, barium and mixtures thereof. Thevalue of “m” which is the mole ratio of M to (Al+E) varies from 0 to1.2. R is a nitrogen containing organic cation and is selected from thegroup consisting of pronated amines, protonated diamines, protonatedalkanolamines, quaternary ammonium ions, diquaternary ammonium ions,quaternized alkanolammonium ions and mixtures thereof. The value of “r”which is the mole ratio of R to (Al+E) varies from about 0.25 to about3.0. The value of “n” which is the weighted average valence of M variesfrom +1 to about +2. The value of “p”, which is the average weightedvalence of the organic cation has a value from about +1 to about +2. Eis an element which is present in the framework and is selected from thegroup consisting of gallium, iron, chromium, indium, boron and mixturesthereof. The value of “x” which is the mole fraction of E varies from 0to about 0.5. The ratio of silicon to (Al+E) is represented by “y” whichvaries from about 5 to about 12, while the mole ratio of O to (Al+E) isrepresented by “z” and” has a value given by the equation:

z=(m·n+r·p+3+4·y)/2.

When M is only one metal, then the weighted average valence is thevalence of that one metal, i.e. +1 or +2. However, when more than one Mmetal is present, the total amount of:

M_(m) ^(n+)=M_(m1) ^((n1)+)+M_(m2) ^((n2)+)+M_(m3) ^((n3)+)+ . . .

and the weighted average valence “n” is given by the equation:$n = {\frac{{m_{1} \cdot n_{1}} + {m_{2} \cdot n_{2}} + {m_{3} \cdot n_{3}} + \ldots}{m_{1} + m_{2} + {m_{3}\quad \ldots}}.}$

Similarly when only one R organic cation is present, the weightedaverage valence is the valence of the single R cation, i.e., +1 or +2.When more than one R cation is present, the total amount of R is givenby the equation:

R_(r) ^(p+)=R_(r1) ^((p1)+)+R_(r2) ^((p2)+)+R_(r3) ^((p3)+)

and the weighted average valence “p” is given by the equation:$p = {\frac{{p_{1} \cdot r_{1}} + {p_{2} \cdot r_{2}} + {p_{3} \cdot r_{3}} + \ldots}{r_{1} + r_{2} + r_{3} + \ldots}.}$

The zeolitic compositions are prepared by a hydrothermal crystallizationof a reaction mixture prepared by combining reactive sources of R,aluminum, silicon and optionally E and/or M in aqueous media.Accordingly, the aluminum sources include, but are not limited to,aluminum alkoxides, precipitated alumina, aluminum hydroxide, aluminumsalt and aluminum metal. Specific examples of aluminum alkoxidesinclude, but are not limited to aluminum ortho sec-butoxide, andaluminum orthoisopropoxide. Sources of silica include but are notlimited to tetraethylorthosilicate, fumed silicas, precipitated silicasand colloidal silica. Sources of the M metals include the halide salts,nitrate salts, acetate salts, and hydroxides of the respective alkali oralkaline earth metals. Sources of the E elements include but are notlimited to alkali borates, boric acid, precipitated galliumoxyhydroxide, gallium sulfate, ferric sulfate, ferric chloride, chromiumchloride, chromium nitrate, indium chloride and indium nitrate. When Ris a quaternary ammonium cation, the sources include the hydroxide, andhalide compounds. Specific examples include without limitationtetramethylammonium hydroxide, tetraethylammonium hydroxide,hexamethonium bromide, tetramethylammonium chloride,methyltriethylammonium hydroxide. R may also be neutral amines,diamines, and alkanolamines. Specific examples are triethanolamine,triethylamine, and N,N,N′,N′ tetramethyl-1,6-hexanediamine.

The reaction mixture containing reactive sources of the desiredcomponents can be described in terms of molar ratios of the oxides bythe formula:

aM_(2/n)O:bR_(2/p)O:(1−c)Al₂O₃ :cE₂O₃ :dSiO₂ :eH₂O

where “a” is the mole ratio of the oxide of M and has a value of 0 toabout 2, “b” is the mole ratio of the oxide of R and has a value ofabout 1.5 to about 30, “d” is the mole ratio of silica and has a valueof about 5 to about 30, “c” is the mole ratio of the oxide of E and hasa value of 0 to about 0.5, and “e” is the mole ratio of water and has avalue of about 30 to about 6000. The reaction mixture is now reacted atreaction conditions including a temperature of about 100° C. to about175° C. and preferably from about 140° C. to about 160° C. for a periodof about 12 hours to about 14 days and preferably for a time of about 2days to about 5 days in a sealed reaction vessel under autogenouspressure. After crystallization is complete, the solid product isisolated from the heterogeneous mixture by means such as filtration orcentrifugation, and then washed with de-ionized water and dried in airat ambient temperature up to about 100° C.

As synthesized, the zeolites will contain some of the exchangeable orcharge balancing cations in its pores. These exchangeable cations can beexchanged for other cations, or in the case of organic cations, they canbe removed by heating under controlled conditions. All of these methodsare well known in the art.

The crystalline zeolites are characterized by a three-dimensionalframework structure of at least SiO₂ and AlO₂ tetrahedral units. Thesezeolites are further characterized by their unique x-ray diffractionpattern. The x-ray diffraction pattern has at least two peaks: one peakat a d-spacing of about 3.9±0.12 Å and one peak at a d-spacing of about8.6±0.20 Å. To allow for ready reference, the different structure typesand compositions of crystalline zeolites have been given arbitrarydesignation of UZM-h, where “h” is an integer starting at one and wherefor example “1” represents a framework of structure type “1”. That isone or more zeolitic composition with different empirical formulas canhave the same structure type “h”, e.g. “1”.

In this respect, the following species can be identified by their x-raydiffraction patterns which have at least the d-spacing and relativeintensities set forth in Tables A to C.

TABLE A UZM-5 2-θ d(Å) I/I_(o) % 6.31-5.89 14.00-15.00 w-m 7.96-7.5811.10-11.65 m-s 10.40-10.01 8.50-8.83 w-m 12.11-11.59 7.30-7.63 m16.10-15.53 5.50-5.70 m-vs 19.28-18.55 4.60-4.78 w-m 22.26-21.603.99-4.11 m 23.20-22.43 3.83-3.96 w-s 24.16-23.33 3.68-3.81 vs30.48-29.55 2.93-3.02 w-m 31.94-30.92 2.80-2.89 w-m 44.83-43.472.02-2.08 w

TABLE B UZM-5P 2-θ d(Å) I/I_(o) % 6.31-5.19 14.00-17.00 w - vs 7.96-7.5611.10-11.70 w - m 10.52-10.04 8.40-8.80 m - s 16.56-15.67 5.35-5.65 w-m19.49-18.87 4.55-4.70 w - m 23.52-22.09 3.78-4.02 w - vs 24.03-23.393.70-3.80 w - vs 30.81-29.76 2.90-3.00 w - m 31.94-30.81 2.80-2.90 w - m45.30-43.04 2.00-2.10 w - m

TABLE B UZM-5P 2-θ d(Å) I/I_(o) % 6.31-5.19 14.00-17.00 w - vs 7.96-7.5611.10-11.70 w - m 10.52-10.04 8.40-8.80 m - s 16.56-15.67 5.35-5.65 w-m19.49-18.87 4.55-4.70 w - m 23.52-22.09 3.78-4.02 w - vs 24.03-23.393.70-3.80 w - vs 30.81-29.76 2.90-3.00 w - m 31.94-30.81 2.80-2.90 w - m45.30-43.04 2.00-2.10 w - m

The zeolite preferably is mixed with a binder for convenient formationof catalyst particles in a proportion of about 5 to 100 mass % zeoliteand 0 to 95 mass-% binder, with the zeolite preferably comprising fromabout 10 to 90 mass-% of the composite. The binder should preferably beporous, have a surface area of about 5 to about 800 m²/g, and berelatively refractory to the conditions utilized in the hydrocarbonconversion process. Non-limiting examples of binders are aluminas,titania, zirconia, zinc oxide, magnesia, boria, silica-alumina,silica-magnesia, chromia-alumina, alumina-boria, silica-zirconia, etc.;silica, silica gel, and clays. Preferred binders are amorphous silicaand alumina, including gamma-, eta-, and theta-alumina, with gamma- andeta-alumina being especially preferred.

The zeolite with or without a binder can be formed into various shapessuch as pills, pellets, extrudates, spheres, etc. Preferred shapes areextrudates and spheres. Extrudates are prepared by conventional meanswhich involves mixing of zeolite either before or after adding metalliccomponents, with the binder and a suitable peptizing agent to form ahomogeneous dough or thick paste having the correct moisture content toallow for the formation of extrudates with acceptable integrity towithstand direct calcination. The dough then is extruded through a dieto give the shaped extrudate. A multitude of different extrudate shapesare possible, including, but not limited to, cylinders, cloverleaf,dumbbell and symmetrical and asymmetrical polylobates. It is also withinthe scope of this invention that the extrudates may be further shaped toany desired form, such as spheres, by any means known to the art.

Spheres can be prepared by the well known oil-drop method which isdescribed in U.S. Pat. No. 2,620,314 which is incorporated by reference.The method involves dropping a mixture of zeolite, and for example,alumina sol, and gelling agent into an oil bath maintained at elevatedtemperatures. The droplets of the mixture remain in the oil bath untilthey set and form hydrogel spheres. The spheres are then continuouslywithdrawn from the oil bath and typically subjected to specific agingtreatments in oil and an ammoniacal solution to further improve theirphysical characteristics. The resulting aged and gelled particles arethen washed and dried at a relatively low temperature of about 50-200°C. and subjected to a calcination procedure at a temperature of about450-700° C. for a period of about 1 to about 20 hours. This treatmenteffects conversion of the hydrogel to the corresponding alumina matrix.

The alkylation and preferably the monoalkylation of aromatic compoundsinvolves reacting an aromatic compound with an olefin using the abovedescribed zeoltic catalyst. The olefins which can be used in the instantprocess are any of those which contain from 2 up to about 20 carbonatoms. These olefins may be branched or linear olefins and eitherterminal or internal olefins. Preferred olefins are ethylene, propyleneand those olefins which are known as detergent range olefins. Detergentrange olefins are linear olefins containing from 6 up through about 20carbon atoms which have either internal or terminal double bonds. Linearolefins containing from 8 to 16 carbon atoms are preferred and thosecontaining from 10 up to about 14 carbon atoms are especially preferred.

The alkylatable aromatic compounds may be selected from the groupconsisting of benzene, naphthalene, anthracene, phenanthrene, andsubstituted derivatives thereof, with benzene and its derivatives beingthe most preferred aromatic compound. By alkylatable is meant that thearomatic compound can be alkylated by an olefinic compound. Thealkylatable aromatic compounds may have one or more of the substituentsselected from the group consisting of alkyl groups (having from 1 toabout 20 carbon atoms), hydroxyl groups, and alkoxy groups whose alkylgroup also contains from 1 up to 20 carbon atoms. Where the substituentis an alkyl or alkoxy group, a phenyl group can also can be substitutedon the alkyl chain. Although unsubstituted and monosubstituted benzenes,naphthalenes, anthracenes, and phenanthrenes are most often used in thepractice of this invention, polysubstituted aromatics also may beemployed. Examples of suitable alkylatable aromatic compounds inaddition to those cited above include biphenyl, toluene, xylene,ethylbenzene, propylbenzene, butylbenzene, pentylbenzene, hexylbenzene,heptylbenzene, octylbenzene, etc.; phenol, cresol, anisole, ethoxy-,propoxy-, butoxy-, pentoxy-, hexoxybenzene, etc.

The particular conditions under which the monoalkylation reaction isconducted depends upon the aromatic compound and the olefin used. Onenecessary condition is that the reaction be conducted under at leastpartial liquid phase conditions. Therefore, the reaction pressure isadjusted to maintain the olefin at least partially dissolved in theliquid phase. For higher olefins the reaction may be conducted atautogenous pressure. As a practical matter the pressure normally is inthe range between about 200 and about 1,000 psig (1379-6985 kPa) butusually is in a range between about 300-600 psig (2069-4137 kPa). Thealkylation of the alkylatable aromatic compounds with the olefins in theC2-C20 range can be carried out at a temperature of about 60° C. toabout 400° C., and preferably from about 90° C. to about 250° C., for atime sufficient to form the desired product. In a continuous processthis time can vary considerably, but is usually from about 0.1 to about3 hr⁻¹ weight hourly space velocity with respect to the olefin. Inparticular, the alkylation of benzene with ethylene can be carried outat temperatures of about 200° C. to about 250° C. and the alkylation ofbenzene by propylene at a temperature of about 90° C. to about 200° C.The ratio of alkylatable aromatic compound to olefin used in the instantprocess will depend upon the degree of selective monoalkylation desiredas well as the relative costs of the aromatic and olefinic components ofthe reaction mixture. For alkylation of benzene by propylene,benzene-to-olefin ratios may be as low as about 1 and as high as about10, with a ratio of 2.5-8 being preferred. Where benzene is alkylatedwith ethylene a benzene-to-olefin ratio between about 1:1 and 8:1 ispreferred. For detergent range olefins of C6-C20, a benzene-to-olefinratio of between 5:1 up to as high as 30:1 is generally sufficient toensure the desired monoalkylation selectivity, with a range betweenabout 8:1 and about 20:1 even more preferred.

The zeolites of this invention can also be used to catalyzetransalkylation. By “transalkylation” is meant that process where analkyl group on one aromatic nucleus is intermolecularly transferred to asecond aromatic nucleus. A preferred transalkylation process is onewhere one or more alkyl groups of a polyalkylated aromatic compound istransferred to a nonalkylated aromatic compound, and is exemplified byreaction of diisopropylbenzene with benzene to give two molecules ofcumene. Thus, transalkylation often is utilized to add to theselectivity of a desired selective monoalkylation by reacting thepolyalkylates invariably formed during alkylation with nonalkylatedaromatic to form additional monoalkylated products. For the purposes ofthis process, the polyalkylated aromatic compounds are those formed inthe alkylation of alkylatable aromatic compounds with olefins asdescribed above, and the nonalkylated aromatic compounds are benzene,naphthalene, anthracene, and phenanthrene. The reaction conditions fortransalkylation are similar to those for alkylation, with temperaturesbeing in the range of about 100 to about 250°, pressures in the range of100 to about 750 psig, and the molar ratio of unalkylated aromatic topolyalkylated aromatic in the range from about 1 to about 10. Examplesof polyalkylated aromatics which may be reacted with, e.g., benzene asthe nonalkylated aromatic include diethylbenzene, diisopropylbenzene,dibutylbenzene, triethylbenzene, triisopropylbenzene etc.

In order to more fully illustrate the invention, the following examplesare set forth. It is to be understood that the examples are only by wayof illustration and are not intended as an undue limitation on the broadscope of the invention as set forth in the appended claims.

EXAMPLE 1

An aluminosilicate reaction mixture was prepared in the followingmanner. Aluminum sec-butoxide (95+%), 58.75 g, was added to 836.34 gTEAOH (35%) with vigorous stirring. To this mixture, 294.73 g colloidalsilica, (Ludox AS-40, 40% SiO₂) was added, followed by the addition of10.18 g distilled water. The reaction mixture was homogenized for 1 hrwith a high-speed mechanical stirrer, and then aged in teflon bottlesovernight at 95° C. After the aging step, the reaction mixture wasrecombined and analyzed; the analysis indicated a silicon content of4.67%.

A 500 g portion of this reaction mixture was treated with TMACl solutionconsisting of 11.77 g TMACl (97%) dissolved in 23.0 g distilled waterwhile applying vigorous mixing. After a half hour of homogenization thereaction mixture was distributed among 8 teflon-lined autoclaves. Theautoclaves were all placed in ovens set at 150° C., where the reactionmixtures were digested for 4 days at autogenous pressures. The solidproducts were recovered by centrifugation, washed, and dried at 95° C.

The composition of the isolated product consisted of the mole ratiosSi/Al=6.88, N/Al=0.83 and C/N=6.05. Scanning Electron Microscopy (SEM)showed the crystallites to consist of clustered platelets approximately100-300 nm across. Characterization by powder X-ray diffraction (XRD)showed the lines in the pattern to be those for the new materialdesignated UZM-5. Table 1 below shows lines characteristic of the phase.A portion of the sample was calcined, by ramping to 540° C. at 2° C./minin N₂, holding at 540° C. in N₂ for 1 hr followed by 7 hr dwell in air,also at 540° C. The BET surface area was found to be 530 m²/g, and themicropore volume was 0.22 cc/g.

TABLE 1 2-θ d(Å) I/I_(o) % 6.24 14.15 m 7.90 11.18 m 10.32 8.57 w-m12.00 7.37 m 15.80 5.60 m-s 16.34 5.42 m 19.05 4.66 w-m 22.00 4.04 m22.86 3.89 m 23.80 3.74 vs 27.40 3.25 w 30.14 2.96 w 30.90 2.89 w 31.602.83 m 33.20 2.70 w 34.56 2.59 w 36.64 2.45 w 44.32 2.04 w

EXAMPLE 2

An aluminosilicate reaction mixture was prepared in the followingmanner: Al(Osec-Bu)₃ (95+%), 116.09 g, was added to 1983.17 g TEAOH(35%) and 1.86 g de-ionized water with vigorous stirring. Then 698.88 gLudox AS-40 was added, with continued stirring. After an hour ofhomogenization, the aluminosilicate reaction mixture was placed inseveral teflon bottle and aged at 95° C. for 3 days. After the agingprocess, elemental analysis showed the mixture contained 5.01% Si andhad a Si/Al ratio of 10.03. This reaction mixture was designated MixtureA. A portion of this aluminosilicate reaction mixture, 40.0 g, wasplaced in a beaker where it was stirred vigorously. Separately, 0.78 gTMACl (97%) was dissolved in 15.0 g de-ionized water. This solution wasadded to the stirring aluminosilicate reaction mixture in a dropwisefashion. The mixture was allowed to homogenize further for about anhour. The reaction mixture was then placed in a teflon-lined autoclaveand digested at 150° C. for 6 days at autogenous pressures. The solidproduct was isolated by centrifugation, washed with de-ionized water,and dried at 95° C.

The product had an x-ray pattern designated to be UZM-6. ScanningElectron Microscopy (SEM) showed the material to consist of plate-likecrystals about 0.1-0.4 μ across and less than 0.05 μ thick. The Si/Alratio of the product UZM-6 was 8.34 by elemental analysis. The BETsurface area of the sample was 520 m²/g, with a micropore volume of 0.21cc/g. Characteristic lines in the x-ray diffraction pattern are given inTable 2.

TABLE 2 2-θ d(Å) I/I_(o) % 6.14 14.83 m 7.76 11.38 m 10.12 8.73 m 11.827.48 m 15.68 5.65 s 16.30 5.43 m 18.98 4.67 m 20.32 4.37 w 21.86 4.06 m22.42 3.96 s 22.78 3.90 m 23.68 3.75 vs 25.24 3.53 w 26.28 3.39 w 26.883.31 m 27.34 3.26 m 29.64 3.01 m 30.08 2.97 w 31.44 2.84 w 33.20 2.70 w44.14 2.05 w

EXAMPLE 3

An aluminosilicate reaction mixture was prepared in an identical mannerto Mixture A described in example 2. However, the reaction mixture wasdetermined to be slightly different by analysis with a Si content of4.79 wt % and a Si/Al ratio of 9.59. A portion of this aluminosilicatereaction mixture, 1100 g, was placed in a large beaker equipped with ahigh-speed stirrer. Separately, a solution was prepared by dissolving4.14 g LiCl and 21.43 g TMACl (97%) in 65 g de-ionized water. Thissolution was added dropwise to the aluminosilicate reaction mixture withstirring and was homogenized for an hour. The reaction mixture was thentransferred to a static 2-L Parr reactor and digested at 150° C. for 3days at autogenous pressure. The solid product was isolated byfiltration, washed with de-ionized water and dried at 95° C.

Powder x-ray diffraction on a sample of the product showed the patternto be consistent with that for UZM-6. The Si/Al ratio was 7.58. The BETsurface area was 512 m²/g, while the micropore volume was found to be0.18 cc/g. SEM of the calcined product showed it to consist of bentplate crystals, sometimes stacked, up to 0.1-0.4 μ across and less that0.05 μ thick. Characteristic lines in the x-ray diffraction pattern aregiven in Table 3.

TABLE 3 2-θ d(Å) I/I_(o) % 6.28 14.07 m 7.84 11.27 s 10.22 8.65 m 11.927.42 m 15.93 5.56 m 18.98 4.67 m 21.98 4.04 w 22.52 3.95 vs 22.92 3.88 m23.76 3.74 vs 26.33 3.38 w 26.92 3.31 m 31.36 2.85 m 33.26 2.69 m 44.242.05 w

EXAMPLE 4

Samples from examples 1 to 3 were tested for alkylation activity byusing an ethylbenzene disproportionation test. The materials wereconverted to the proton form before testing. The UZM-6 from example 3was calcined in air at 350° C. for 1.5 hours, 450° C. for 1.5 hours and7 hours at 580° C. and ion exchanged with ammonium chloride, three timesat 80° C. for 2 hours The UZM-6 from example 2 was calcined at 520° C.for 1 hour in N₂, followed by 19 hours in air. The UZM-5 from example 1was calcined at 520° C. for 10 hr. The calcined samples were sized to40-60 mesh and loaded (250 mg) into a quartz tube (11 mm i.d.) reactorresiding in a furnace. The outlet pressure at the reactor inlet wasatmospheric pressure. The samples were pretreated at 250° C. in a flowof N₂. The temperature was brought down to 150° C. and then the feed wasintroduced. The feed consisted of the N₂ flow passing through anethylbenzene saturator held at 0° C., with the N₂ flow controlled at 150cc/min. While the flow remained constant, the sample was exposed to thefeed and reaction products were examined at 150° C., 150° C., 125° C.,175° C., 200° C., 230° C., and 175° C. The product effluents areanalyzed by an on-line GC to measure activity and selectivity. Resultsfrom the second 150° C. and the 230° C. product collections are given inTable 4.

TABLE 4 UZM-5, Ex. 1 UZM-6, Ex. 2 UZM-6, Ex. 3 Temperature 150 230 150230 150 230 (deg C.) Flow Rate 150 150 150 150 150 150 (cc/min)Methane/Ethane 0.02 0 0.03 0.06 0 0.08 C4's 0 0 0.02 0.07 0.1 0.11Benzene 0.09 0.18 0.39 1.21 0.64 2.63 Ethylcyclohexane 0 0 0 0 0 0Toluene 0 0 0.04 0.04 0.04 0.05 Ethylbenzene 99.72 99.46 98.69 96.0297.86 91.97 p-Xylene 0 0 0 0 0 0 m-Xylene 0 0 0 0 0 0 o-Xylene 0 0 0 0 00 1E4MBZ 0 0 0 0 0 0 1E3MBZ 0 0 0 0 0 0 1E2MBZ 0 0 0 0 0 0 13DEBZ 0.090.22 0.41 1.63 0.76 3.24 14DEBZ 0.08 0.13 0.4 0.82 0.55 1.6 12DEBZ 0 00.03 0.15 0.05 0.28 14DIPBZ 0 0 0 0 0 0.02 135TEBZ 0 0 0 0 0 0 124TEBZ 00 0 0 0 0 EB CONV 0.28 0.54 1.31 3.98 2.14 8.03

EXAMPLE 5

This example demonstrates the capability of UZM-6 to catalyze thesynthesis of ethylbenzene from benzene and ethylene. The zeolite fromexample 3 was converted to the proton by the same procedure as inexample 4. The zeolite was then bound with Plural SB alumina in a 70%zeolite/30% alumina formulation and formed into {fraction (1/16)}″diameter extrudates. The extrudates were then calcined at 550° C. for 2hr. The test employs a ⅞″ diameter stainless steel reactor which isloaded with 40 cc of the catalyst. The benzene and ethylene are mixedon-line to a 3/1 benzene/ethylene ratio and then pre-heated beforeentering the reactor. The olefin was added at a rate of 0.45 hr⁻¹ LHSV.The testing was done with an effluent recycle to control the free olefinat the reactor inlet. The reaction was carried out at 500 psig. Activityand selectivity data were collected at 200° C. and 230° C. Theselectivities to alkylated products are shown in Table 5.

TABLE 5 Ethylbenzene Synthesis with UZM-6 Hours on Stream 60 271 Inlettemperature 200° C. 230° C. Ethylbenzene 80.31 74.95 Diethylbenzenes16.26 19.95 Triethylbenzenes 2.46 3.92 Tetraethylbenzenes 0.22 0.37Alkylated products 99.25 99.19

What is claimed is:
 1. A process for monoalkylating aromatic compoundscomprising reacting under alkylation conditions and under at leastpartial liquid phase conditions an olefin with an alkylatable aromaticcompound in the presence of a catalyst to provide an alkylated compound,the catalyst comprising a crystalline aluminosilicate zeolite having acomposition in the as synthesized form on an anhydrous basis in terms ofmole ratios of the elements of: M_(m) ^(n+)R_(r)^(p+)Al_((1−x))E_(x)Si_(y)O_(z) where M is at least one exchangeablecation selected from the group consisting of alkali and alkaline earthmetals, “m” is the mole ratio of M to (Al+E) and varies from about 0 toabout 1.2, R is a nitrogen-containing organic cation selected from thegroup consisting of protonated amines, protonated diamines, protonatedalkanolamines, quaternary ammonium ions, diquaternaryammonium ions,quaternized alkanolamines and mixtures thereof, “r” is the mole ratio ofR to (Al+E) and has a value of about 0.25 to about 3.0, E is an elementselected from the group consisting of Ga, Fe Cr, In and B, “x” is themole fraction of E and varies from 0 to 0.5, “n” is the weighted averagevalence of M and has a value of about +1 to about +2, “p” is theweighted average valence of R and has a value of +1 to about +2, “y” isthe mole ratio of Si to (Al+E) and varies from about 5 to about 12 and“z” is the mole ratio of O to (Al+E) and has a value determined by theequation: z=(m·n+r·p+3+4·y)/2 the zeolite characterized in that it hasat least two x-ray diffraction peaks, one at a d-spacing of 3.9±0.12 Åand one at 8.6±0.2 Å.
 2. The process of claim 1 where the zeolite has ax-ray powder diffraction pattern which contains at least the d-spacingsand relative intensities of one of Tables A to C.
 3. The process ofclaim 1 where M is selected from the group consisting of lithium,cesium, sodium, potassium, strontium, barium, calcium, magnesium andmixtures thereof and R is a quaternary ammonium ion.
 4. The process ofclaim 3 where the quaternary ammonium compound is selected from thegroup consisting of tetramethylammonium, tetraethylammonium,tetrapropylammonium, hexamethonium, diethyldimethylammonium,ethyltrimethylammonium and mixtures thereof.
 5. The process of claim 3where M is sodium and the quaternary ammonium cation is a mixture oftetraethylammonium and tetramethylammonium.
 6. The process of claim 3where M is lithium and the quaternary ammonium cation is a mixture oftetraethylammonium and tetramethylammonium.
 7. The process of claim 1where M is a mixture of an alkali metal and an alkaline earth metal andR is a quaternary ammonium cation.
 8. The process of claim 7 where M isa mixture of lithium and strontium.
 9. The process of claim 7 where thequaternary ammonium compound is selected from the group consisting oftetramethylammonium, tetraethylammonium, hexamethonium,tetrapropylammonium, diethyldimethylammonium, ethyltrimethylammonium andmixtures thereof.
 10. The process of claim 1 where the olefin containsfrom 2 up to about 20 carbon atoms.
 11. The process of claim 10 wherethe olefin contains from 6 up to about 20 carbon atoms.
 12. The processof claim 11 where the olefin contains from about 10 up to about 14carbon atoms.
 13. The process of claim 1 where the alkylatable aromaticcompound is selected from the group consisting of benzene, naphthalene,anthracene, phenanthrene, and substituted derivatives thereof.
 14. Theprocess of claim 13 where the alkylatable aromatic compound is benzene.15. The process of claim 1 where the alkylatable aromatic compound is analkyl-, hydroxyl, or alkoxy-substituted benzene, naphthalene,anthracene, or phenanthrene, where the alkyl or alkoxy group containsfrom 1 up to about 20 carbon atoms.
 16. The process of claim 1 where thereaction conditions Include a temperature from about 60° C. up to about400° C. and a reaction pressure from about 200 up to about 1000 psig.17. A process for preparing cumene by the alkylation of benzene withpropylene comprising reacting propylene with benzene at a temperaturebetween about 90° C. and about 200° C. at a pressure sufficient tomaintain at least a partial liquid phase in the presence of a catalystcomprising a crystalline aluminosilicate zeolite having a composition inthe as synthesized form on an anhydrous basis in terms of mole ratios ofthe elements of: M_(m) ^(n+)R_(r) ^(p+)Al_((1−x))E_(x)Si_(y)O_(z) whereM is at least one exchangeable cation selected from the group consistingof alkali and alkaline earth metals, “m” is the mole ratio of M to(Al+E) and varies from about 0 to about 1.2, R is a nitrogen-containingorganic cation selected from the group consisting of protonated amines,protonated diamines, protonated alkanolamines, quaternary ammonium ions,diquaternaryammonium ions, quaternized alkanolamines and mixturesthereof, “r” is the mole ratio of R to (Al+E) and has a value of about0.25 to about 3.0, E is an element selected from the group consisting ofGa, Fe, Cr, In and B, “x” is the mole fraction of E and varies from 0 to0.5, “n” is the weighted average valence of M and has a value of about+1 to about +2, “p” is the weighted average valence of R and has a valueof +1 to about +2, “y” is the mole ratio of Si to (Al+E) and varies fromabout 5 to about 12 and “z” is the mole ratio of O to (Al+E) and has avalue determined by the equation: z=(m·n+r·p+3+4·y)/2 the zeolitecharacterized in that it has at least two x-ray diffraction peaks, oneat a d-spacing of 3.9±0.12 Å and one at 8.6±0.2 Å.
 18. The process ofclaim 17 where the zeolite has a x-ray powder diffraction pattern whichcontains at least the d-spacings and relative intensities of one ofTables A to C.
 19. The process of claim 17 where the reactiontemperature is from about 90° C. up to about 160° C.
 20. The process ofclaim 17 where the pressure is from about 200 up to about 1000 psig.